Highly compatible and non-migratory polymeric uv-absorber

ABSTRACT

The present invention relates to highly compatible hydroxyphenyltriazine UV-absorbers and to their use in organic polymers, especially for protecting the contents of transparent plastic packages such as pharmaceuticals, cosmetics, personal care products, shampoos and the like, and especially foodstuffs such as beverages, fresh vegetables or meat, from the deleterious effects of ultraviolet radiation. Especially advantageous is the combined use of a UV absorber and an oxygen scavenger. It has been found that certain highly compatible tris-aryl-s-triazines are especially effective towards this end when incorporated in the containers or films in which such materials are stored.

The present invention relates to highly compatible hydroxyphenyltriazineUV-absorbers and to organic polymer material, especially thermoplasticpolymer films, containing them. The polymer material thus obtained maybe used as packaging films, protecting packed foodstuffs, beverages,pharmaceuticals, cosmetics, personal care products, shampoos and thelike from the deleterious effects of ultraviolet radiation. It isfurther useful in protecting plants in greenhouses. The inventionfurther pertains to a method of preventing photooxidation of packed foodby combined use of a UV absorber and an oxygen scavenger. It has beenfound that certain tris-aryl-s-triazines are especially effective whenincorporated in the containers or films in which such materials arestored. Compounds of present invention are further effective in cosmeticformulations for the protection of human (or animal) skin or hairagainst UV radiation.

Also many packaged products such as certain fruit juices, soft drinks,beer, wines, food products, dairy products, cosmetics, shampoos,vitamins and pharmaceuticals are deleteriously affected, i.e. degraded,by the effects of ultraviolet (UV) light when packaged in plasticcontainers which allow the transmission of such light.

The use of UV absorbers towards protecting bottle and film contents iswell known. However there is a trend towards the use of clear or lightlycolored containers. More aesthetically pleasing containers may be formedfrom clear plastics, which also allow one to view the contents.Unfortunately, clear and lightly colored containers and films allow thetransmission of significant portions of ultraviolet light, i.e. light inthe range of about 280 to about 400 nm. Further, there is a trendtowards more light-weight and hence thinner walled containers.Thin-walled containers, by virtue of a shorter path length, will allowmore UV light to pass. Due to these trends in packaging there is a needfor more efficient UV absorbers for use in this area.

Many cooking oils and salad oils are now offered in clear PET[poly(ethylene terephthalate)] packaging. Practically all vegetable orseed-based oils such as soybean, olive, safflower, cottonseed and cornoils contain varying levels of unsaturated olefinic acids or esters(e.g. linoleates), which are susceptible to light-induced degradation.Most plant-based oils also contain natural chlorophyll or other pigmentphotosensitizers. Pascall et al., J. Food Sci., 60 (5), 1116 (1995),discuss the UV protection of soybean oil with the use of Tinuvin® 326incorporated into coextruded, multi-layered, polypropylene-basedcontainers. Tinuvin® 326 is a benzotriazole UV absorber,5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole,available from Ciba Specialty Chemicals Corp.

WO 03/004557 describes some hydroxyphenyltriazine UV absorbers havinggood persistency in polyolefin films. Plastic containers or filmscontaining durable UV absorbers are also mentioned in WO 01/57124.

Present hydroxyphenyl triazine UV absorbers show excellent compatibilityand persistence in a variety of plastic materials and protect thesematerials from the harmful effects of UV radiation. The same time, theseUV absorbers provide efficient and selective UV shielding in greenhousefilms, window sheets and packaging materials. Due to extremely longalkyl moieties they are highly compatible with many polymers, allowingthus to incorporate higher amounts of UVA. They are thermally stable anddo not exude from the polymer, which is important when in contact withfood or beverages.

The present invention relates to a oligo- or polyester formula (I)-[A-O-D-O]_(x)—  (I)in whichx is a number from 1 to 50;A is a group of the formula (II)

or has one of the meanings given for T;D is C₄-C₁₂ alkylene or said alkylene substituted by OH or interruptedby O or both substituted by OH and interrupted by O;L is C₁-C₁₈alkylene; C₅-C₁₂cycloalkylene; C₃-C₁₈alkenylene; or one ofsaid residues substituted by phenyl, C₇-C₁₁alkylphenyl,C₅-C₁₂cycloalkyl, OH, halogen, C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy,C₃-C₁₈alkenyloxy, COOH;the R₁ are independently of each other H, OR₇ or OH, with the provisothat at least one of R₁ or R₁₃ is OH;the R₇ are independently of each other hydrogen, C₁-C₁₂alkyl or aradical of formula -L-CO—O—R₉;R₉ is H, C₁-C₁₈alkyl, C₂-C₁₂hydroxyalkyl;R₁₀ is hydrogen, C₁-C₄alkyl, Cl, phenyl or a group —OR₇;R₁₁ is hydrogen or methyl;R₁₃ is hydrogen, methyl, OH or OR₇; andT is the divalent acyl residue of an aliphatic or cycloaliphaticdicarboxylic acid of 13 to 60 carbon atoms;and which contains at least one moiety of formula (II) and at least onemoiety T.

In a preferred compound, L is C₁-C₄alkylene, especially C₂-C₄alkylideneor methylene. D is advantageously C₄-C₁₂alkylene or C₄-C₁₀alkyleneinterrupted by O.

T as the divalent acyl residue of an aliphatic or cycloaliphaticdicarboxylic acid of 13 to 60 carbon atoms includes, for example,aliphatic diacyls wherein the 2 carbonyl groups are interconnected byC₁₁-C₅₈alkylene or -alkenylene or alkylene interrupted by cycloalkyleneor cycloalkenylene, each of which is unsubstituted or substituted byalkyl, and containing 11 to 58 carbon atoms in total, preferably 20 to50 carbon atoms. Alkylene or alkenylene may be branched or unbranched,or, preferably not adjacent to an ethylenic double bond, interrupted byoxygen. In preferred compounds, T is —CO-T′-CO—, wherein T′ isC₂₀-C₅₀alkylene or C₂₀-C₅₀alkylene interrupted by one or more oxygenatoms; especially preferred is unbranched C₂₀-C₅₀alkylene. In furtherpreferred compounds, T is —CO-T′-CO—, wherein T′ is alkylene interruptedby C₅-C₁₂cycloalkylene or C₅-C₁₂cycloalkenylene or said cycloalkylene orcycloalkenylene substituted by alkyl and containing 11 to 58 carbonatoms, especially 20-50 carbon atoms, in total; especially preferredcycloalkylene is cyclohexylene; especially preferred cycloalkenylene is,cyclohexenylene. Valuable spacer groups T′ are, for example, of theformula IX

wherein R₂₀ is —(C_(b)H_(2b))— and R₂₁ is —(C_(c)H_(2c))— andR₂₂, R₂₃ and R₂₄ are —(C_(d)H_(2d))—H, —(C_(o)H_(2o))—H, and—(C_(f)H_(2f))—H, respectively, where a is from the range 0-7, and eachof the indices b-f is from the range 0-20,with the condition that the sum a+b+c+d+e+f is from the range 15-45,or of the formula X

whereinR₂₅ and R₂₆ each are C₁-C₁₈alkylene and each of R₂₇, R₂₈, R₂₉ and R₃₀,independently, are H or C₁-C₁₈alkyl, and R₂₉ and R₃₀ together may alsobe a chemical bond, with the condition that the total number of carbonatoms in formula X ranges from 20 to 50.Of special technical importance are spacer groups T′ of the formula Xwherein R₂₅ and R₂₆ independently are alkylene of 4-12 carbon atoms,each of R₂₇ and R₂₈, independently, are C₄-C₁₂alkyl, while R₂₉ and R₃₀are hydrogen.

Suitable diacids may be obtained, for example, by dimerization of amono- with a di-unsaturated fatty acid; the product containing acycloalkenyl structure may be used as such or is, preferably,hydrogenated before use in the preparation of the present compounds; inthe latter case, the hydrogenated diacid often is a mixture of openchain (“alkylene”) type and cycloalkylene-interrupted compounds. Anexample for the preparation of a diacid from fatty acids A and B isgiven in the following scheme:

In the compounds of present formula I, most preferably, the R₁ are OH;

the R₇ are hydrogen or methyl;

R₁₀ is hydrogen, methyl or a group —OR₇;

R₁₁ is hydrogen;

R₁₃ is hydrogen, OH or methyl.

Terminal groups of the oligomer or polymer of formula (I) usually are

—O-D-OR₁₂, or —OR₁₂ if bonded to A (left side of formula I),

or -A-OR₁₂, such as -T′-COOR₁₂ or -[formula II]-OR₁₂, or —R₁₂ if bondedto O (right side of formula I),

where R₁₂ is H or C₁-C₈alkyl.

For example, the ester of formula (I) may conform to the formula (III)

in whichx is a number from 1 to 20;the number y is at least 1 and ranges from (x+z−1) to (x+z+1);z is a number from 1 to 20; andR₈ is hydrogen, C₁-C₁₂alkyl; C₅-C₁₂cycloalkyl; C₂-C₁₂alkenyl; phenyl;C₇-C₁₁alkylphenyl; C₁-C₁₂alkyl substituted by phenyl, OH, halogen;C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₁₈alkenyloxy or COOH; especiallyhydrogen or C₁-C₄alkyl;R₁₂ is hydrogen or C₁-C₈alkyl;R₁₈ is hydrogen or C₁-C₄alkyl;D is C₄-C₈alkylene or C₄-C₁₀alkylene interrupted by O; and T′ isC₂₀-C₅₀alkylene or C₂₀-C₅₀alkylene interrupted by one or more oxygenatoms;and all other symbols are as defined for formula I above.

T′ may also be alkylene interrupted by C₅-C₁₂cycloalkylene or saidcycloalkylene, especially cyclohexylene, substituted by alkyl andcontaining 20-50 carbon atoms in total.

In the oligo- or polyester of formula (III), each of the divalentstructural units identified by the indices x and z bond to thestructural unit —O-D- Identified by the index y, and/or to an end groupR₁₂ or OR₁₂.

In compounds of the formula (I), x is preferably from the range 2-50,more preferably from the range 2-20, especially 4-12; the number oftriazine moieties of the formula II to diacid residues T preferablyranges from about 1:3 to about 10:1, more preferably from about 1:1 toabout 5:1. In compounds of the formula (III), each of x and z arepreferably from the range 1-16; more preferably, x is from the range1-10 and z is ranging from 2-12.

Oligomeric or polymeric esters of the invention such as those of formulaI or III usually have a molecular weight within the range 1000 to 50000g/mol, more preferably 1500 to 20000 g/mol, most preferably 2000 to10000 g/mol (number average Mn as determined by gel permeationchromatography GPC).

Alkylphenyl is alkyl-substituted phenyl; C₇-C₁₄alkylphenyl embracesexamples such as methylphenyl(tolyl), dimethylphenyl(xylyl),trimethylphenyl(mesityl), ethylphenyl, propylphenyl, butylphenyl,dibutylphenyl, pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl.

Phenylalkyl is phenyl-substituted alkyl; C₇-C₁₁phenylalkyl embracesexamples such as benzyl, α-methylbenzyl, α-ethylbenzyl,α,α-dimethylbenzyl, phenylethyl, phenylpropyl, phenylbutyl andphenylpentyl.

Alkyl interrupted by O can generally comprise one or more nonadjacentoxygen atom(s). Preferably, a carbon atom of an alkylene chain such as Dor T′ bonds to not more than 1 heteroatom.

Within the scope of the stated definitions, the alkyl radicals arebranched or unbranched alkyl such as methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl,isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl,1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl and octadecyl.

Alkylene such as of L or D derives from such alkyls by abstraction of anhydrogen atom.

Within the scope of the stated definitions, the alkenyl radicals includeallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl,n-penta-2,4-dienyl, 3-methyl-but-2-enyl; n-oct-2-enyl, n-dodec-2-enyl,isododecenyl, n-octadec-2-enyl and n-octadec-4-enyl.

The heavy chains of T, e.g. alkylene groups of T′, may have a certainmolecular distribution around their main component. Ranges may be, forexample, from 22-26, 28-32 or 34-38 C-atoms. It is however also possiblethat broader ranges are used such as for example from 20 to 40, from 30to 50 or from 30 to 40 carbon atoms, each for T′ in total.

Since the educts for preparing a compound of formula (I) or (III) arecommercial products, they may vary within certain specifications. Thisis particularly the case for high molecular weight diacids from whichthe T groups are derived, when T is C₂₀-C₆₀alkylene (which may beinterrupted as described above).

Commercially available diacids or diacid esters may also contain smallamounts of chains below C₂₀. Therefore mixtures of compounds wherein Tis a mixture containing up to 10% of diacyl chains below 20 carbon atomsand 90 to 100% of diacyl chains between 20 and 60, particularly between20 and 40 carbon atoms are also subject of the invention. Percentage isweight percent, based on the total mixture.

The compounds of formula (I) and (III) or precursors thereof can beprepared in analogy to methods described in WO 03/004557 or publicationsmentioned therein (e.g. EP-A-434 608, H. Brunetti and C. E. Lüthi, Helv.Chim. Acta 55, 1566 (1972), U.S. Pat. No. 3,118,887, EP-A-165608).

(Poly)esters of formula (I) or (III) are advantageously preparedstarting from tris-aryl-triazines containing 2 carboxylic acid groups orsuitable derivatives thereof such as acid chloride, anhydride orespecially ester groups. Such educts or their homologues are described,inter alia, in U.S. Pat. No. 4,826,978, U.S. Pat. No. 5,736,597 (seee.g. columns 11-13), U.S. Pat. No. 5,686,233, U.S. Pat. No. 5,959,008(see e.g. col. 30, line 35, until col. 31, line 11) and a further eductof the same type, e.g. aliphatic, cycloaliphatic or aromaticdicarboxylic acid or derivative thereof containing the group T. Foresterification, the dicarboxylic educts are preferably reacted accordingto methods known in the art with suitable amounts, e.g. 0.9-1.1 mol permol dicarboxyl or equimolar amounts, of a diol HO-D-OH; preferred diolsinclude glycol, glycerine, various polyethylene glycoles, orα,ω-dihydroxyalkanes of various chain lengths such as butanediol,pentanediol, hexanediol, heptanediol, octanediol, nonanediol,decanediol, undecanediol, dodecanediol, tridecanediol, pentadecanediol,octadecanediol, eicosanediol, and mixtures thereof. Reaction can becarried out with or without addition of further components such assolvents (e.g. aliphatic alcohols, ethers, aromatic hydrocarbons orhalogenated hydrocarbons such as chlorobenzene, or solvent mixtures) orcatalysts, e.g. transesterification catalysts such as mineral or organic(Lewis or Broensted-type) acids or bases. In case that no additionalsolvent is used, an educt such as the diol or a suitable ester of adicarboxylic acid may be used in excess and serve simultaneously as asolvent. Temperature and pressure are usually not critical, thus, thereaction often is carried out at temperatures in the range −5° C. to200° C., e.g. between 10 and 170° C., and pressure close to 1atmosphere, e.g. 10⁴ to about 10⁶ Pa, with or without presence ofoxygen, e.g. under nitrogen or argon.

Present invention also pertains to an oligoester or polyester which isobtained by reacting a tris-aryl-triazine of the formula V

and a compound of the formula R₁₂—O-T-O—R₁₂,where Y is CO and all other all symbols are as defined above, with adiol HO-D-OH.

Present invention also pertains to a composition protected against thepermeation of ultraviolet radiation comprising

-   -   (a) an organic polymer material, e.g. a synthetic thermoplastic        polymer, and    -   (b) at least one compound of formula (I) or a mixture thereof.

A further subject of the invention is a transparent plastic container orfilm, which protects against the deleterious effects of ultravioletradiation, and which comprises

-   -   (a) a transparent, e.g. clear or lightly colored, plastic, and    -   (b) at least one compound of formula (I) or a mixture thereof.

Definitions and preferences for the compounds of formula (I) are asgiven above.

Examples for containers are bottles, boxes, blisters or cups, which maybe sealed by thick walled materials or, for example, by films. Thecontainer may be fully transparent or partly transparent; in such cases,the present compound of the formula I usually is present at least in thetransparent part, e.g. the film sealing of a pigmented cup. Examples forgoods packed in such containers include food and beverages, cosmeticarticles, medicals and pharmaceutic preparations, etc.

Especially in the case of greenhouse films, the present composition mayfurther contain growth promoters, such as component (b) of thecompositions disclosed in EP-A-1413599, while present compound of theformula I may be employed as the UVA (component c1 of EP-A-1413599) inthese systems.

The compounds are useful for many kinds of plastic materials from whichcontainers, sheets, films and woven or nonwoven fabrics can be made.Examples are given below.

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene,polyvinylcyclohexane, polylsoprene or polybutadiene, as well as polymersof cycloolefins, for instance of cyclopentene or norbornene,polyethylene (which optionally can be crosslinked), for example highdensity polyethylene (HDPE), high density and high molecular weightpolyethylene (HDPE-HMW), high density and ultrahigh molecular weightpolyethylene (HDPE-UHMW), medium density polyethylene (MDPE), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

-   -   a) radical polymerisation (normally under high pressure and at        elevated temperature).    -   b) catalytic polymerisation using a catalyst that normally        contains one or more than one metal of groups IVb, Vb, VIb or        VIII of the Periodic Table. These metals usually have one or        more than one ligand, typically oxides, halides, alcoholates,        esters, ethers, amines, alkyls, alkenyls and/or aryls that may        be either π-or σ-coordinated. These metal complexes may be in        the free form or fixed on substrates, typically on activated        magnesium chloride, titanium(III) chloride, alumina or silicon        oxide. These catalysts may be soluble or insoluble in the        polymerisation medium. The catalysts can be used by themselves        in the polymerisation or further activators may be used,        typically metal alkyls, metal hydrides, metal alkyl halides,        metal alkyl oxides or metal alkyloxanes, said metals being        elements of groups Ia, IIa and/or IIIa of the Periodic Table.        The activators may be modified conveniently with further ester,        ether, amine or silyl ether groups. These catalyst systems are        usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta),        TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers(e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers,where the 1-olefin is generated in-situ; propylene/butadiene copolymers,isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acidcopolymers and their salts (ionomers) as well as terpolymers of ethylenewith propylene and a diene such as hexadiene, dicyclopentadiene orethylidene-norbornene; and mixtures of such copolymers with one anotherand with polymers mentioned in 1) above, for examplepolypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetatecopolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA),LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbonmonoxide copolymers and mixtures thereof with other polymers, forexample polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructureincluding syndiotactic, isotactic, hemi-isotactic or atactic; whereatactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromaticmonomers including styrene, α-methylstyrene, all isomers of vinyltoluene, especially p-vinyltoluene, all isomers of ethyl styrene, propylstyrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, andmixtures thereof. Homopolymers and copolymers may have anystereostructure including syndiotactic, isotactic, hemi-isotactic oratactic; where atactic polymers are preferred. Stereoblock polymers arealso included.

6a. Copolymers including aforementioned vinyl aromatic monomers andcomonomers selected from ethylene, propylene, dienes, nitriles, acids,maleic anhydrides, maleimides, vinyl acetate and vinyl chloride oracrylic derivatives and mixtures thereof, for example styrene/butadiene,styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkylmethacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkylmethacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methylacrylate; mixtures of high impact strength of styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene/propylene/diene terpolymer; and block copolymers of styrenesuch as styrene/butadiene/styrene, styrene/isoprene/styrene,styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6.), especially includingpolycyclohexylethylene (PCHE) prepared by hydrogenating atacticpolystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation ofpolymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure includingsyndiotactic, isotactic, hemi-isotactic or atactic; where atacticpolymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene orα-methylstyrene, for example styrene on polybutadiene, styrene onpolybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styreneand acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,acrylonitrile and methyl methacrylate on polybutadiene; styrene andmaleic anhydride on polybutadiene; styrene, acrylonitrile and maleicanhydride or maleimide on polybutadiene; styrene and maleimide onpolybutadiene; styrene and alkyl acrylates or methacrylates onpolybutadiene; styrene and acrylonitrile on ethylene/propylene/dieneterpolymers; styrene and acrylonitrile on polyalkyl acrylates orpolyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadienecopolymers, as well as mixtures thereof with the copolymers listed under6), for example the copolymer mixtures known as ABS, MBS, ASA or AESpolymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated and brominated copolymer of isobutylene-isoprene(halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene,copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinylcompounds, for example polyvinyl chloride, polyvinylidene chloride,polyvinyl fluoride, polyvinylidene fluoride, as well as copolymersthereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinylacetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates(PMMA), polyacrylamides and polyacrylonitriles, impact-modified withbutyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; ethylenevinylalcohol copolymers (EVOH); as well as their copolymers with olefinsmentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids,polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate(PAN), biodegradable polylactones, and polyhydroxybenzoates, as well asblock copolyether esters derived from hydroxyl-terminated polyethers;and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The compounds of the invention are useful for many kinds of plasticmaterials from which containers, sheets, films and woven or nonwovenfabrics can be made. Preferred polymer materials, e.g. for films orplastic containers, are a polyolefin, a polyester, a polyvinylalcohol, apolyvinylacetate or a polycarbonate; most preferred, especially for foodpackaging films or containers, are polyethylenetherephthalate (PET) andpolyolefins, in particular polyethylene (PE), polypropylene (PP), lowdensity polyethylene (LDPE), linear low density polyethylene (LLDPE),(VLDPE) and (ULDPE). More preferred materials for sheets arepolycarbonate, a polyamide, a polyacryl, or transparent ABS, especiallypolycarbonate.

Most advantageously, the composition of the invention is a plasticcontainer or film used as a food or medical packaging material;preferably the thickness of the film is from 10μ to 200μ, morepreferably from 20μ to 80μ, and of the plastic container from 200μ to1000μ. Preferably, the compound of formula (I) is present in an amountof from 0.005% to 10%, based on the weight of the plastic material.

Preferably, the organic polymer material is a plastic container or filmor sheet wherein the plastic material is transparent, for instance clearor lightly colored.

Especially in case of polyesters, the organic polymer materialadvantageously may contain an additive for the reduction of acetaldehydecontent (see, for example, WO 01/02489, WO 01/23475, WO 02/53643,EP-A-1239006, WO 03/16401) and/or an optical brightener (fluorescentwhitener; in analogy to known systems, see, for example, U.S. Pat. No.5,985,389, U.S. Pat. No. 6,166,852). Suitable optical brightenersinclude, inter alia, compounds of the stilbene, coumarin andbis-benzoxazole classes known for this application and available, interalia, under the trade names Blankophor®, Eastman®, Fluolite®, Hostalux®,Leukopur®, Uvitex®, Whitefluor®, Eccowhite® from several manufacturers;suitable compounds are, for example, those of CAS Nos. 91-44-1(4-methyl-7-diethylaminocoumarin);

53850-91-2 (3-phenyl-7-(4-methyl-6-butyloxybenzoxazole)coumarin);

5089-22-5; 5242-49-9; 3333-62-8; 40470-686; and especially:

7128-64-5 (2,5-bis(5-tert-butyl benzoxazol-2-yl)thiophene) and/or

1533-45-5 (4,4′-bis(benzoxazol-2-yl)stilbene.

The present UV absorbers may also be incorporated into optical lenses orglasses, such as acryl glasses, or coatings thereon. Preferred materialsfor optical lenses and glasses, e.g. for sunglasses, are acrylics orpolycarbonate, especially polymethyl methacrylate (PMMA). A furtherimportant application is in solar control films or architecturalglazings (see, e.g. U.S. Pat. No. 6,166,852, U.S. Pat. No. 6,191,199).

Preferably, the thickness of the sheet may vary between about 0.5 to 8mm, e.g. for solid sheets, to about 3 to 100 mm, e.g. for twin ormultiple wall sheets.

Alongside the stabilizer of the invention, the plastic material of theinvention may also include other stabilizers or other additives, such asa phenolic antioxidant, a sterically hindered amine and/or a phosphiteor phosphonite. Examples for further stabilizers and additives are givenbelow.

1. Antioxidants

1.1. Alkylated monophenols, for example2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol,2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol,2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol,2-(α-methylcyclohexyl)-4,6-dimethylphenol,2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linearor branched in the side chains, for example,2,6-di-nonyl-4-methylphenol,2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol,2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol,2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example2,4-dioctylthiomethyl-6-tert-butylphenol,2,4-dioctylthiomethyl-6-methylphenol,2,4-dioctylthiomethyl-6-ethylphenol,2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol,2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenylstearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol),4,4′-thiobis(6-tert-butyl-3-methylphenol),4,4′-thiobis(6-tert-butyl-2-methylphenol),4,4′-thiobis-(3,6-di-se-amylphenol),4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

1.6. Alkylidenebisphenols, for example2,2′-methylenebis(6-tert-butyl-4-methylphenol),2,2′-methylenebis(6-tert-butyl-4-ethylphenol),2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)-phenol],2,2′-methylenebis(4-methyl-6-cyclohexylphenol),2,2′-methylenebis(6-nonyl-4-methylphenol),2,2′-methylenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(4,6-di-tert-butylphenol),2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol),2,2′-methylenebis[6-α-methylbenzyl)-4-nonylphenol],2,2′-methylenebis[6-(α,α-dimethylbenzyl)₄-nonylphenol],4,4′-methylenebis(2,6-di-tert-butylphenol),4,4′-methylenebis(6-tert-butyl-2-methylphenol),1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)₄-methylphenol,1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane,ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene,bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate,1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane,1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, for example3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine,bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate,bis(3,5-di-tert-butyl hydroxybenzyl)sulfide,isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates, for exampledioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example1,3,5-tris-(3,5-di-tert-butyl hydroxybenzyl)-2,4,6-trimethylbenzene,1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine Compounds, for example2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine,1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates, for exampledimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide,4-hydroxystearanilide, octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or poly-hydric alcohols, e.g. with methanol, ethanol,n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols, e.g. with methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol,tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide,3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide(Naugard®XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (Vitamin C)

1.19. Aminic antioxidants, for exampleN,N′-di-isopropyl-p-phenylenediamine,N,N′-di-sec-butyl-p-phenylenediamine,N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine,N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,N,N′-bis(1-methylheptyl)-p-phenylenediamine,N,N′-dicyclohexyl-p-phenylenediamine, N,N′-diphenyl-p-phenylenediamine,N,N′-bis(2-naphthyl)-p-phenylenediamine,N-isopropyl-N′-phenyl-p-phenylenediamine,N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine,N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine,N-cyclohexyl-N′-phenyl-p-phenlenediamine,4-(p-toluenesulfamoyl)diphenylamine,N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine, diphenylamine,N-allyldiphenylamine, 4-isopropoxydiphenylamine,N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,N-phenyl-2-naphthylamine, octylated diphenylamine, for examplep,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol,4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol,4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine,2,6-di-tert-butyl-4-dimethylaminomethyl-phenol,2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane,N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane,1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino) propane,(o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine,tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines, a mixture of mono- and dialkylateddodecyldiphenylamines, a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylatedtert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine,phenothiazine, a mixture of mono- und dialkylatedtert-butyl/tert-octyl-phenothiazines, a mixture of mono- und dialkylatedtert-octyl-phenothiazines, N-allylphenothiazin,N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene,N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV Absorbers and Light Stabilisers

2.1. 2-(2′-Hydroxyphenyl)benzotriazoles, for example2-(2′-hydroxy-5′-methylphenyl)-benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)₅-chloro-benzotriazole,2-3′-tert-butyl-2′-hydroxy-5′-methylphenyl-5-chloro-benzotriazole,2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)benzotriazole,2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole,2-3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole,2-3′,5′-bis-(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole,2-3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole,2-3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole,2,2′-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazolewith polyethylene glycol 300; [R—CH₂CH₂—COO—CH₂CH₂

₂ where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl,2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole;2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxyand 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as forexample 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenylsalicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol,benzoyl resorcinol, 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl3,5-di-tert-butyl-hydroxybenzoate, octadecyl3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctylα-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methylα-cyano-β-methyl-p-methoxy-cinnamate, butylα-cyano-β-methyl-p-methoxy-cinnamate, methylα-carbomethoxy-p-methoxycinnamate andN-(β-carbomethoxy-βcyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine, nickeldibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. themethyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

2.6. Sterically hindered amines, for examplebis(2,2,6,6-tetramethyl-piperidyl)sebacate,bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, linear or cyclic condensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine,tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate,1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cycliccondensates ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane, the condensate of2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane,8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, amixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product ofN,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine aswell as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.[136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, areaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decaneund epichlorohydrin,1,1-bis(1,2,2,6,6-pentamethyl-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine,diester of 4-methoxy-methylenemalonic acid with1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of maleicacid anhydride-α-olefin-copolymer with2,2,6,6-tetramethyl-4-aminopiperidine or1,2,2,6,6-pentamethyl-4-aminopiperidine,5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone; of specialimportance, especially for use in films such as greenhouse films, arebis(2,2,6,6-tetramethyl piperidyl)sebacate;bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate;

the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid (CAS-No. 65447-77-0);

N,N′,N″,N′″-tetrakis(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)amino)triazin-2-yl)-4,7-diazadecane-1,10-diamine(CAS-No. 106990-43-6);

(Chimassorb® 2020, CAS No. 192268-64-7),

where n or n′ is mainly from the range 3-5; or mixtures of thesecompounds.

2.7. Oxamides, for example 4,4′-dioctyloxyoxanilide,2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide,2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide,N,N′-bis(3-dimethylaminopropyl)oxamide,2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- andp-methoxy-disubstituted oxanilides and mixtures of o- andp-ethoxy-disubstituted oxanilides.

2.8. Further 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-3,5-triazine,2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]4,6-bis(2,4-dimethyl)-1,3,5-triazine,2-(2-hydroxy-4-[2-ethylhexyl)oxy)phenyl)-4,6-di(4-phenylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-[2-heptylcarbonyloxyethoxy]phenyl)-4,6-diphenyl-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-(2-ethylhexyl)oxy)phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine,2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine,2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.

3. Metal deactivators, for example N,N′-diphenyloxamide,N-salicylal-N′-salicyloyl hydrazine, N,N′-bis(salicyloyl)hydrazine,N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine,3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide,N,N′-diacetyladipoyl dihydrazide, N,N′-bis(salicyloyl)oxalyldihydrazide, N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite,diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite,diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,diisodecyloxypentaerythritol diphosphite,bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)4,4′-biphenylenediphosphonite,6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite,bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin,2,2′,2″-nitrilo[triethyltris(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite],2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite,5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphlrane.

Especially preferred are the following phosphites:Tris(2,4-di-tert-butylphenyl)phosphite (Irgafos® 68, Ciba-Geigy),tris(nonylphenyl)phosphite,

5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,N-hexadecyl-alpha-pentadecyl-nitrone,N-octadecyl-alpha-heptadecyl-nitrone,N-hexadecyl-alpha-heptadecyl-nitrone,N-ocatadecyl-alpha-pentadecyl-nitrone,N-heptadecyl-alpha-heptadecyl-nitrone,N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived fromN,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearylthiodipropionate.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid,for example the lauryl, stearyl, myristyl or tridecyl esters,mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zincdibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritoltetrakis(β-dodecylmercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate, antimony pyrocatecholate or zinkpyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum,metal oxides such as titanium dioxide or magnesium oxide, phosphates,carbonates or sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and the salts thereof,e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodiumsuccinate or sodium benzoate; polymeric compounds such as ioniccopolymers (ionomers). Especially preferred are1,3:2,4-bis(3′,4′-dimethylbenzylidene)sorbitol,1,3:2,4-di(paramethyldibenzylidene)sorbitol, und1,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica,barium sulfate, metal oxides and hydroxides, carbon black, graphite,wood flour and flours or fibers of other natural products, syntheticfibers.

13. Other additives, for example, oxygen absorbers, acetaldehydescavengers, plasticisers, processing aids, lubricants, emulsifiers,clarifyers, pigments, rheology additives, catalysts, flow-controlagents, optical brighteners, flameproofing agents, antistatic agents andblowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312;U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611;DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,343,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

The nature and amount of the further stabilizers added are determined bythe nature of the substrate to be stabilized and its intended use; inmany cases from 0.01 to 5% by weight is used, based on the polymer to bestabilized.

Of certain technical importance is the addition of a processing aid,e.g. a fluoro elastomer, which may prevent the formation of depositsduring or after extrusion of the cast film. These processing aids areoften added in an amount of 0.1 to 2%, typically 0.2-1%, relative to theweight of the base polymer (for example: polyethylene). Thus, a typicalLLDPE formulated according to the present invention contains, besidesthe compound of the formula I, about 500 ppm of of a fluoro elastomer,such as Dynamar® FX9614 (available from 3M).

The plastic container or film may also additionally contain an oxygenabsorber, especially an iron based additive as oxygen absorber (oxygenscavenger).

It has been found that the freshness of food sealed in a transparentfood package with use of an oxygen absorber may be unexpectedlyenhanced, when the transparent packaging material contains a UVabsorber: After packing under normal atmosphere or modified atmospherewith reduced oxygen partial pressure (using vacuum or inert gases suchas nitrogen, carbon dioxide, argon) and air tight sealing, the scavengeracts with reducing the partial pressure of oxygen by the time to aharmless level. Depending on parameters like type of oxygen absorberemployed, temperature, package dimensions, this induction periodtypically lasts between several hours and several days, during whichoxidation processes may continue to alter the properties of the food,especially by fast photooxidation reactions. By blocking the major partof UV light with a UV absorber within the transparent container wall,photooxidation may be prevented and the protection gap during theinduction period closed. Fruit and vegetables and, especially, freshfood of high protein and/or fat content such as meat, fish, diaryproducts etc., may thus be kept longer on the shelf and retain betterquality and appearance.

A further subject of the invention therefore is a sealed foodpackage orcontainer comprising a transparent, especially clear or lightly colouredsheet or film made from plastic material, characterized in that

-   -   a) the plastic material contains a UV absorber, and    -   b) the package further comprises an oxygen scavenger.

The UV absorber in the plastic material is selected fromhydroxyphenyl-s-triazines, 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones and mixtures thereof, such as compounds listedabove under sections 2.1, 2.2 and 2.8 and compounds of present formula(I); especially preferred are hydroxyphenyl-s-triazines such ascompounds of the formula (I) described above, as well as the compounds2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole,2-(2-hydroxy-5-methylphenyl)-benzotriazole,2-(2-hydroxy-3,5-di-t-butylphenyl)-benzotriazole,2-hydroxy-4-octyloxybenzophenone,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-(2-hydroxy-octyloxyphenyl)-4,6-di(4-phenylphenyl)-1,3,5-triazine.

Advantageously, type and amount of UV absorber (a) is sufficient toreduce the daylight UV radiation in the package to a level causingsubstantially no photooxidation within the induction time of the oxygenscavenger (b), especially by reducing the light intensity transmittedthrough the transparent polymeric material in the range 280-380 nm to10% or less, especially to 5% or less.

Depending on the exact type of UV absorber used and the desired blockingeffect, the UV absorber incorporated into the transparent film orcontainer wall advantageously results in 0.01 to 10 g, e.g. about 0.05to about 5 g, especially 0.1-1 g, of UV absorber per m² of film or wall.

Packaging films or sheets of the invention often contain more than onelayer, at least one layer thereof containing the UV-absorber of formulaI (multilayer material, see below)

The polymeric material is preferably as described above for compositionscontaining the compound of formula (I), e.g. selected from polyester,polyolefin or ethylene-vinylacetate copolymer. The polymeric materialmay comprise one or more further additives, e.g. selected fromclarifiers, phenolic antioxidants, phosphites and phosphonites, metaloxides and hydrotalcites, fluorescent brighteners, plasticisers,carboxylic acid salts such as stearates.

The transparent polymeric material often is a packaging film or UVshielding film of 10-200 μm thickness, or a wall of a plastic container.The oxygen scavenger (b) may be incorporated in the transparentpolymeric material or in another part of the package or storedseparately in the package.

Consequently, the invention further pertains to a method of preventingphotooxidation of packed food, characterized in that the food is sealedin a package comprising a transparent, especially clear or lightlycoloured, container or film made from plastic material, wherein theplastic material contains a UV absorber, and

the package further contains an oxygen scavenger, and to

the use of an oxygen scavenger and transparent plastic container or filmcontaining a UV absorber as a food packaging material protecting thepacked food from photooxidation.

Oxygen absorbers to be used according to present invention may be knowncomponents including compounds or systems described in U.S. Pat. Nos.5,364,555; 4,536,409; 4,702,966; 5,605,996; 5,866,649; 5,096,724;5,202,052; 94/09,084; 6,162,806; 6,083,585; 6,346,308; 6,406,766;6,506,463; 6,509,436; 5,955,527; 5,639,815; 5,627,239; 5,641,825;5,660,761; 5,736,616; 5,744,246; 5,776,361; 5,859,145; 6,139,770;6,323,288; 6,333,087; 5,744,056; 6,369,148; 5,021,515; 5,049,624;5,239,016; 5,952,066; 5,759,653; 6,210,601; 6,290,871; 5,981,676;6,133,352; 6,143,197; 6,214,254; 6,254,802; 6,387,461; 6,139,770;5,958,254; 6,346,200; 6,517,728; 6,410,156; 6,423,776; 6,479,160;5,176,849; 5,211,875; 5,310,497; 5,346,644; 5,350,622; 5,425,896;5,492,742; 5,529,833; 5,648,020; 5,798,055; 5,811,027; 6,284,153;6,391,406; 6,465,065; 5,744,056; 5,885,481; 6,369,148; or in thepublications WO 98/04,558; WO 01/29,116; WO 01/88,023; WO 00/37,321; WO98/12,127; WO 99/15,432; WO 99/15,433; US-A-2001-0023025; WO 95/02,616;WO 95/04,776; WO 96/08,371; WO 96/40,799; WO 99/48,963; WO 00/011,972;WO 01/90,202; WO 01/90,238; WO 02/28,944; WO 02/33,024; WO 02/36,670; WO02/57,328; US-A-2002-0037377; US-A-2002-0022144; WO 96/18,685; WO96/18,686; US-A-2002-0063238; WO 00/64,775; WO 01/34,479; WO 01/03,521;WO 99/10,251; WO 02/051,825; WO 02/076,916; WO 01/89,830;US-A-2002-0099125; US-A-2003-0036605; WO 97/32,925; WO 98/12,250; WO98/53,026; WO 91/17,044, including purely organic systems (e.g. based onsalicylic acid, lactic acid, amines etc.); or systems based on anoxidizable metal component (e.g. the metals Fe, Zn, Co, Al, Mg, Cu, Sn,or oxidizable alloys, salts, complexes or metal-organic compoundsthereof) and optional auxiliaries such as electrolytes, phosphates,binders, acidifiers. Use and incorporation of the oxygen scavenger mayfollow the method described in the literature, respectively.

Preferably, the oxygen scavenger is an additive based on an oxidizableiron or iron compound, e.g. as disclosed in U.S. Pat. No. 5,744,056;U.S. Pat. No. 5,885,481; U.S. Pat. No. 6,369,148.

The additives of the invention and optional further components may beadded to the polymer material individually or mixed with one another. Ifdesired, the individual components can be mixed with one another beforeincorporation into the polymer for example by dry blending, compactionor in the melt.

The incorporation of the additives of the invention and optional furthercomponents into the polymer is carried out by known methods such as dryblending in the form of a powder, or wet mixing in the form ofsolutions, dispersions or suspensions for example in an inert solvent,water or oil. The additives of the invention and optional furtheradditives may be incorporated, for example, before or after molding oralso by applying the dissolved or dispersed additive or additive mixtureto the polymer material, with or without subsequent evaporation of thesolvent or the suspension/dispersion agent. They may be added directlyinto the processing apparatus (e.g. extruders, internal mixers, etc),e.g. as a dry mixture or powder or as solution or dispersion orsuspension or melt.

The incorporation can be carried out in any heatable container equippedwith a stirrer, e.g. in a closed apparatus such as a kneader, mixer orstirred vessel. The incorporation is preferably carried out in anextruder or in a kneader. It is immaterial whether processing takesplace in an inert atmosphere or in the presence of oxygen, provided thatthe oxygen scavenger, if present, is not deactivated.

The addition of the additive or additive blend to the polymer can becarried out in all customary mixing machines in which the polymer ismelted and mixed with the additives. Suitable machines are known tothose skilled in the art. They are predominantly mixers, kneaders andextruders.

The process is preferably carried out in an extruder by introducing theadditive during processing.

Particularly preferred processing machines are single-screw extruders,contrarotating and corotating twin-screw extruders, planetary-gearextruders, ring extruders or cokneaders. It is also possible to useprocessing machines provided with at least one gas removal compartmentto which a vacuum can be applied.

Suitable extruders and kneaders are described, for example, in Handbuchder Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W.Knappe, H. Potente, 1989, pp. 3-7, ISBN:3446-14339-4 (Vol. 2Extrusionsanlagen 1986, ISBN 3-446-14329-7).

For example, the screw length is 1-60 screw diameters, preferably 35-48screw diameters. The rotational speed of the screw is preferably 10-600rotations per minute (rpm), very particularly preferably 25-300 rpm.

The maximum throughput is dependent on the screw diameter, therotational speed and the driving force. The process of the presentinvention can also be carried out at a level lower than maximumthroughput by varying the parameters mentioned or employing weighingmachines delivering dosage amounts.

If a plurality of components are added, these can be premixed or addedindividually. The additives of the invention and optional furtheradditives can also be sprayed onto the polymer material. They are ableto dilute other additives (for example the conventional additivesindicated above) or their melts so that they can be sprayed alsotogether with these additives onto the material. Addition by sprayingduring the deactivation of the polymerization catalysts is particularlyadvantageous; in this case, the steam evolved may be used fordeactivation of the catalyst. In the case of spherically polymerizedpolyolefins it may, for example, be advantageous to apply the additivesof the invention, optionally together with other additives, by spraying.

The additives of the invention and optional further additives can alsobe added to the polymer in the form of a masterbatch (“concentrate”)which contains the components in a concentration of, for example, about1% to about 40% and preferably 2% to about 20% by weight incorporated ina polymer. The polymer must not be necessarily of identical structurethan the polymer where the additives are added finally. In suchoperations, the polymer can be used in the form of powder, granules,solutions, suspensions or in the form of latices.

Incorporation can take place prior to or during the shaping operation,or by applying the dissolved or dispersed compound to the polymer, withor without subsequent evaporation of the solvent. In the case ofelastomers, these can also be stabilized as latices. A furtherpossibility for incorporating the additives of the invention intopolymers is to add them before, during or directly after thepolymerization of the corresponding monomers or prior to crosslinking.In this context the additive of the invention can be added as it is orelse in encapsulated form (for example in waxes, oils or polymers).

In a specific embodiment the plastic container or film or sheet is amultilayer construction of 2 to 7 polymer layers containing the UVabsorber of the invention or a mixture thereof in at least 1 layer. Inthis case, the polymer composition of the invention may contain arelatively large amount of the compatible hydroxyphenyltriazinestabilizer, for example 1-15% by weight, and is applied or incorporatedin a thin layer (e.g. 5-100μ) to a shaped article made from a polymercontaining little or no stabilizer of the invention, e.g. a film.Application can be made at the same time as the shaping of the basearticle, for example by coextrusion. Alternatively, application can bemade to the base article after it has been shaped, for example bylamination with a film or by coating with a solution. The external layeror layers of the finished article has or have the function of a UVfilter which protects the interior of the article and/or inner layer(s)against UV light.

Still a further subject of the invention is the use of a compound offormula (I) or (III) or a mixture thereof which is incorporated into aplastic container or film or sheet, for content protection of packagedfoodstuffs, beverages, pharmaceuticals, cosmetics or personal careproducts.

The following examples illustrate the invention. All parts orpercentages, in the examples as in the remainder of the description andin the claims, are by weight, unless stated otherwise. Room temperaturedenotes a temperature in the range 20-30° C., unless stated otherwise.Data given for elemental analysis are in % by weight calculated (cal) orexperimentally measured (exp) for the elements C, H and N. In theexamples, the following abbreviations are used:

-   % W/W percent by weight;-   l litre;-   m.p. melting point or range;-   PP polypropylene;-   LDPE low density polyethylene;-   DSC differential scan calorimetry;-   NMR nuclear magnetic resonance (of ¹H, if not otherwise indicated);-   ε at λ_(max) molar extinction coefficient (l⁻mol⁻¹cm⁻¹) at long    wavelength UV absorption maximum;-   Mn number average of molecular mass (g/mol) as determined by GPC;-   GPC gel permeation chromatography;-   PDI polydispersity (ratio of mass and number average of molecular    weight).

In the following examples, the molecular weight parameters (Mn, Mw, PDI)are determined by GPC (Gel Permeation Chromatography). The GPCmeasurements are carried out on a Perkin Elmer LC 50 liquidchromatograph equipped with a reflective index Perkin Elmer LC 30 andthe data are calculated by using a Perkin Elmer software (TurboSEC). AllGPC measurements are carried out by using 0.02 M di-ethanol-aminesolution in chromatographic grade tetrahydrofuran (THF) as solvent at45° C. The columns used are PLGEL (Polymer Laboratories) 300 mm×7.5 mm,stationary phase 3 mm Mixed E, supplied by Polymer Laboratories.Polystyrene standards are used for the calibration curve. Visual meltingpoints and melting ranges are measured by using a Gallenkamp equipment.The extinction coefficients (e) are calculated by recording the UVspectra of the products in methylene chloride or toluene solutions on aPerkin Elmer Lambda 2S spectrophotometer.

A: PREPARATION EXAMPLE Example A1

In a reaction flask 103.59 g (0.18 mol) of monomer (A), 35.4 g (0.3 mol)of 1,6-hexanediol, 68.4 g (0.12 mol) of dimer acid hydrogenated and 2 gof p-toluene sul-phonic acid are added in 210 ml of xylene. The mixtureis refluxed for 9 hours and xylene, water and methanol are distilledoff. The reaction mass is cooled to 120° C. and 750 ml of xylene areadded. The solution is cooled at 80° C. and washed four times withwater. The or-ganic layer is then dried under vacuum, yielding a productwith melting range 80-92° C.

Example A2

In a reaction flask 103.59 g (0.18 mol) of monomer (A), 35.4 g (0.3 mol)of 1,6-hexanediol, 68.4 g (0.12 mol) of the above cycloalkylene diacid(CAS 68783-41-5; isomer mixture; available from Cognis or Sigma) and 2 gof p-toluene sulphonic acid are added in 210 ml of xylene. The mixtureis refluxed for 9 hours and xylene, water and methanol are distilledoff. The reaction mass is cooled to 120° C. and 750 ml of xylene areadded. The solution is cooled at 80° C. and washed four times withwater. The organic layer is then dried under vacuum, yielding a productwith melting range 80-92° C.

The educt of CAS No. 68783-41-5 is a mixture of compounds; besides themajor educt shown In the scheme above, it usually contains open chainand/or unsaturated components, the molecular weight ranging from about562 to about 566 g/mol.

Example A3

In a reaction flask 57.50 g (0.10 mol) of monomer (A), 17.70 g (0.15mol) of 1,6-hexanediol, 28.50 g (0.05 mol) of the above cycloalkylenediacid (CAS 68783-41-5; isomer mixture; available from Cognis or Sigma)and 1.2 g of p-toluene sulphonic acid are added in 100 ml of xylene. Themixture is refluxed for 10 hours and xylene, water and methanol aredistilled off. The reaction mass is cooled to 120° C. and 500 ml ofxylene are added. The solution is cooled at 80° C. and washed four timeswith water. The organic layer is then dried under vacuum, yielding aproduct with melting range 90-99° C.

B: APPLICATION EXAMPLES Example B1

17 g of the product of the example A2 is mixed with 983 g of milledLLDPE (Dowlex® NG 5056E, supplied by Dow Chemical, characterized by adensity of 0.919 g/cm³ and a melt flow index (190° C./2.16 kg) of 1.1).The mixture is extruded at 230° C. in a OMC® twin-screw extruder.Granules obtained are blown (Formac® lab-scale blow extruder) at 230° C.to a film of about 50 μm thickness.

A UV-Vis spectrum is recorded from the film in the range 200-800 nm(Perkin-Elmer lambda 20 spectrophotometer, equipped with a RSA-PE-20Labsphere Integrating sphere), showing a broad absorption maximum atabout 336 nm; transmittance and integrated transmittance data are shownin the following table. Wavelength (nm) 315 365 280-370 280-390 400-700Transmittance (%) 2.0 5.2 3.2 8.1 92

Another film sample is prepared correspondingly without UV absorber forcomparison purposes (blank film), showing a transmittance of 93% in therange 400-700 nm.

The film of the invention shows the following further properties:Yellowness Index difference vs. blank film (ASTN E 313-96): 1.5 Hazevalue (ASTM D 1003-61): 8.6%

The polymer composition of the invention shows good UV absorption,excellent transmittance of visible light and low yellowing and haze.

Example B2

20 g of the product of the example A3 is processed in the sameconditions as in example B1 to give a LLDPE film of about 50 μmthickness.

The UV-Vis spectrum recorded from the film in the range 200-800 nm showsa broad absorption maximum at about 337 nm. The transmittance andintegrated transmittance data determined as in example B1 are shown inthe following table. Wavelength (nm) 315 365 280-370 280-390 400-700Transmittance (%) 1.0 2.2 1.5 5.1 91

The film of the invention shows the following further properties:Yellowness Index difference vs. blank film (ASTM E 313-96): 1.8 Hazevalue (ASTM D 1003-61): 14.3%

The polymer composition of the invention shows excellent UV absorption,good transmittance of visible light and low yellowing and haze.

Example B3

13 g of the product of the example A2 is mixed with 6 g of micronizedzinc oxide or 2 g of micronized titanium dioxide respectively and with981 g or 985 g respectively of milled LLDPE and then processed in thesame conditions of the previous examples to give films of about 50 μmthickness.

The integrated transmittance data and the haze values determined as inthe previous examples are shown in the following table. Wavelength (nm)% T 280-390 % T 400-700 % Haze 1.3% ex. A2 + 0.6% ZnO 9.9 91 13.8 1.3%ex. A2 + 0.2% TiO₂ 9.9 91 14.1

The polymer composition of the invention shows good UV absorption, goodtransmittance of visible light and low haze.

Example B4

The product of the example A2 is utilized in the preparation of anindustrial mult-layer extrusion cast film. Such a film is made of 5layers, having the following structure and composition, going from onesurface to the other (the approximate thickness of each layer isreported into brackets):

-   -   LLDPE (Dowlex® NG 5056E, Dow Chemical) containing 1.7% by weight        of the product of example A2 (20 μm)    -   Adhesive layer (Admer® NF518E, Mitsui Chemicals, 3 μm)    -   EVOH (type F171B, Eval Europe) barrier layer (10 μm)    -   Adhesive layer (Admer® NF518E, Mitsui Chemicals, 3 μm)    -   LLDPE (Dowlex° NG 5056E, Dow Chemical) containing 1.7% by weight        of the product of example A2 (20 μm)

Another film sample is prepared correspondingly without UV absorber forcomparison purposes (blank film).

The integrated transmittance data determined as in the previous examplesare shown in the following table. Wavelength (nm) 280-370 280-390400-700 Transmittance (%) 8.8 14.6 92

The film of the invention shows the following further properties:Yellowness Index difference vs. blank film (ASTM E 313-96): 0.5 Hazevalue (ASTM D 1003-61): 3.6%

The polymer composition of the invention shows good UV absorption,excellent transmittance of visible light very low yellowing and minimalhaze.

Example B5

In order to assess the positive effect of the shielding of the UVradiation from the polymer compositions of the invention on the storageof edible goods, the polymer composition of the example B1 is used forthe following experiment, where a piece of boiled ham is placed inside apackaging constituted in the following manner: the packaging is made ofa glass container with inlet and outlet valves for gas purging and aquartz cover that can be hermetically sealed. An atmosphere containing2% of oxygen is fluxed inside the container and the film with thepolymer composition of example B1 is placed on top of the quartz cover.The container is placed at 5° C. under four fluorescent lamps of type“cool white”. After 4 days, the color index a* (ASTM E 313-96) of theham is measured with a calorimeter, as compared to a film packaged andstored in the same conditions, but without UV screening. The result isreported in the following table: sample a* index 1.7% ex. A2 −5.2 blankfilm −9.3

The ham packed under the film of the invention retains the red shade ofthe meat distinctly better than the ham packed under a conventional film(blank film).

Example B6

The barrier 6-layer film of example B4 is used as a food packaging filmin the following experiment. Pieces of boiled ham are stored in glasscontainers open on the top (diameter 105 mm, height 60 mm, named A, Band C, respectively) and equipped with inlet and outlet valves for gaspurging.

Container A is covered with the barrier film described in example B4(film of the Invention containing the UVA of example A2). The film isplaced on the top of the container and silicon-sealed. An atmospherecontaining 5% of oxygen is fluxed inside the packaging. About 200 cm² ofthe interior side walls are coated with a 125 μm thick extrusion castLDPE film (6401, Dow Chemicals) containing 50% of the oxygen scavengerShelfplus® O₂, in order to further reduce the oxygen level in thepackage.

Shelfplus® O₂ is an iron based oxygen scavenger available from CibaSpecialty Chemicals.

Container B (comparative sample) is sealed with a blank barrier filmhaving the same structure and composition as the film of container A,but without UVA product in it. The interior side walls of container Bare coated with the same film as the film used for container A. Theatmosphere inside the packaging is the same as that of container A.

Container C (comparative sample) is sealed with the blank film used forcontainer B, but the film on turn is covered by a black piece ofcardboard, so that no light can enter into the packaging. The interiorside walls of container C are coated with the same film as the film usedfor container A. The atmosphere inside the packaging is the same as thatof container A.

The containers are stored at 5° C. under four “cool white” fluorescentlamps; the appearence of the packed ham is evaluated with respect ofchanges in visual aspects and color.

The ham packed according to the invention retains the red shade of themeat distinctly better than the ham packed under a conventional film (B,blank film).

1. An oligoester or polyester of formula (I)-[A-O-D-O]_(x)—  (I) in which x is a number from 1 to 50; A is a groupof the formula (II)

or has one of the meanings given for T; D is C₄-C₁₂ alkylene or saidalkylene substituted by OH or interrupted by O or both substituted by OHand interrupted by O; L is C₁-C₁₈alkylene, C₅-C₁₂cycloalkylene,C₃-C₁₈alkenylene, or one of said residues substituted by phenyl,C₇-C₁₁alkylphenyl, C₅-C₁₂cycloalkyl, OH, halogen, C₁-C₁₈alkoxy,C₅-C₁₂cycloalkoxy, C₃-C₁₈alkenyloxy, or COOH; the R₁ groups areindependently of each other H, OR₇ or OH, with the proviso that at leastone of R₁ or R₁₃ is OH; the R₇ groups are independently of each otherhydrogen, C₁-C₁₂alkyl or a radical of formula -L-CO—O—R₉; R₉ is H,C₁-C₁₈alkyl or C₂-C₁₂hydroxyalkyl; R₁₀ is hydrogen, C₁-C₄alkyl, Cl,phenyl or a group —OR₇; R₁₁ is hydrogen or methyl; R₁₃ is hydrogen,methyl, OH or OR₇; and T is the divalent acyl residue of an aliphatic orcycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms; and whichcontains at least one moiety of formula (II) and at least one moiety T.2. Oligoester or polyester of claim 1, wherein D is C₄-C₁₂alkylene orC₄-C₁₀alkylene interrupted by O; L is C₁-C₄alkylene; T is the divalentacyl residue CO-T′-CO, wherein T′ is C₂₀-C₅₀alkylene or C₂₀-C₅₀alkyleneinterrupted by one or more oxygen atoms, or is alkylene interrupted byC₅-C₁₂cycloalkylene or by C₅-C₁₂cycloalkenylene, each of which isunsubstituted or substituted by alkyl, and T′ contains 20-50 carbonatoms in total; the R₇ groups are hydrogen or methyl; R₁₀ is hydrogen,methyl or a group —OR₇; R₁₁ is hydrogen; and R₁₃ is hydrogen, OH ormethyl.
 3. Oligoester or polyester of claim 1 conforming to the formula(III)

in which x is a number from 1 to 20; the number y is at least 1 andranges from (x+z−1) to (x+z+1); z is a number from 1 to 20; and R₈ ishydrogen, C₁-C₁₂alkyl, C₅-C₁₂cycloalkyl, C₂-C₁₂alkenyl, phenyl,C₇-C₁₁alkylphenyl, C₁-C₁₂alkyl substituted by phenyl, OH or halogen;C₁-C₁₈alkoxy, C₅-C₁₂cycloalkoxy, C₃-C₁₈alkenyloxy or COOH; R₁₂ ishydrogen or C₁-C₈alkyl; R₁₈ is hydrogen or C₁-C₄alkyl; D isC₄-C₈alkylene or C₄-C₁₀alkylene interrupted by O; and T′ isC₂₀-C₅₀alkylene or C₂₀-C₅₀alkylene interrupted by one or more oxygenatoms, or is alkylene interrupted by C₅-C₁₂cycloalkylene or byC₅-C₁₂cycloalkenylene, each of which is unsubstituted or substituted byalkyl, with T′ containing 20-50 carbon atoms in total.
 4. Oligoester orpolyester of claim 1, wherein x is from the range 2-50, and the numberof triazine moieties of the formula II to divalent acid residues T isbetween 1 to 3 and 10 to
 1. 5. A process for the preparation of anoligoester or polyester of formula (III) according to claim 3, whichprocess comprises reacting a tris-aryl-triazine of the formula (V)

and a compound of the formula R₁₂—O—OC-T′-CO—O—R₁₂ with a diol of theformula HO-D-OH, where Y is CO.
 6. Composition protected against thepermeation of ultraviolet radiation comprising (a) an organic polymermaterial and (b) at least one oligoester or polyester of formula (I) ofclaim 1 or a mixture thereof.
 7. Composition of claim 6, which is atransparent plastic container or film or multilayer film.
 8. Compositionof claim 6 wherein the organic polymer material is a polyolefin, apolyester, a polyvinylalcohol, a polyvinylacetate, a polylactone or apolycarbonate.
 9. Composition of claim 6 wherein the organic polymermaterial is a film of 10μ to 200μ thickness or a plastic container of200μ to 1000μ wall thickness, and containing the compound of formula (I)in an amount of from 0.005% to 10%, based on the weight of the organicpolymer material.
 10. Composition of claim 6 containing a furthercomponent selected from phenolic antioxidants, sterically hinderedamines, further UV absorbers, phosphites or phosphonites, alkali metalsalts or alkaline earth metal salts of higher fatty acids, fillers,metal oxides, hydrotalcites, oxygen scavengers, acetaldehyde scavengers,plasticisers, clarifiers, lubricants, emulsifiers, pigments, rheologyadditives, catalysts, flow-control agents, processing aids, opticalbrighteners, flameproofing agents, antistatic agents and blowing agents.11. A method of protecting a transparent plastic container or film andits contents against the deleterious effects of ultraviolet radiation,which method comprises incorporation of an oligoester or polyester ofclaim 1 into said plastic container or film.
 12. (canceled)
 13. A methodof preventing photooxidation of packed food, characterized in that thefood is sealed in a transparent plastic container or film or multilayerfilm, which container or film or multilayer film comprises at least oneoligoester or polyester of formula (I) according to claim 1 and anoxygen scavenger.
 14. A method of preventing photooxidation of packedfood, characterized in that the food is sealed in a package or containercomprising a transparent sheet or film made from plastic material,wherein the plastic material contains a UV absorber selected from thehydroxyphenyl-s-triazines, 2-(2′-hydroxyphenyl)benzotriazoles,2-hydroxybenzophenones, and mixtures thereof, and further contains anoxygen scavenger.
 15. Method of claim 14, wherein the plastic materialcomprises a polyolefin, a polyester, a polyvinylalcohol, apolyvinylacetate or a polycarbonate.
 16. Method of claim 14, wherein theUV absorber is used in an amount from 0.01 g to 10 g per square meter oftransparent sheet or film.
 17. Method of claim 14, wherein and theoxygen scavenger is an additive based on oxidizable iron or anoxidizable iron compound.